Unraveling Conformer-Specific Sources of Hydroxyl Radical Production from an Isoprene-Derived Criegee Intermediate by Deuteration.

Ozonolysis of isoprene, the most abundant volatile organic compounds emitted into the Earth's troposphere after methane, yields three distinct Criegee intermediates. Among these, methyl vinyl ketone oxide (MVK-oxide) is predicted to be the major source of atmospheric hydroxyl radicals (OH) from isoprene ozonolysis. Previously, Barber et al. [ J. Am. Chem. Soc., 2018, 140, pp 10866-10880] demonstrated that syn-MVK-oxide conformers undergo unimolecular decay via 1,4-hydrogen (H) transfer from the methyl group to the adjacent terminal oxygen atom, followed by the prompt release of OH radical products. Here, we selectively deuterate the methyl group of MVK-oxide (d3-MVK-oxide) and record its IR action spectrum in the vinyl CH stretch overtone (2νCH) region. The resultant time-dependent appearance of OD radical products, detected by laser-induced fluorescence, demonstrates that a unimolecular decay of d3-MVK-oxide proceeds by an analogous 1,4-deuterium (D) atom transfer mechanism anticipated for syn conformers. The experimental spectral and temporal results are compared with the calculated IR absorption spectrum and unimolecular decay rates predicted by the Rice-Ramsperger-Kassel-Marcus (RRKM) theory for syn-d3-MVK-oxide, as well as the prior study on syn-MVK-oxide. The d3-MVK-oxide IR action spectrum is similar to that for MVK-oxide, yet exhibits notable changes as the overtone and combination transitions involving CD stretch shift to a lower frequency. The unimolecular decay rate for d3-MVK-oxide is predicted to be a factor of 40 times slower than that for MVK-oxide in the 2νCH region. Experimentally, the temporal profile of the OD products reflects the slower unimolecular decay of d3-MVK-oxide compared to that for MVK-oxide to OH products as well as experimental factors. Both experiment and theory demonstrate that quantum mechanical tunneling plays a very important role in the 1,4-H/D-transfer processes at energies in the vicinity of the transition-state barrier. The similarities of the IR action spectra and changes in the unimolecular decay dynamics upon deuteration indicate that syn conformers make the main contribution to the IR action spectra of MVK-oxide and d3-MVK-oxide.

Rational Design of New Dihydrobenzooxophosphole-Based Lewis Base Organocatalysts.

A series of new dihydrobenzooxophosphole-based Lewis Base organocatalysts were designed and synthesized. They are demonstrated effective in trichlorosilane-mediated stereoselective conjugate reductions of C=C bonds. DFT calculations reveal that the strong hydrogen bond between the amide linker and the chloride on silicon in the transition state contributes to the high reactivity of the catalyst 3a.

[Contrast-enhanced ultrasound and liver imaging: review of the literature]. / Performance de l'échographie de contraste en pathologie hépatique: synthèse de la littérature.

The advent of second-generation microbubble ultrasound contrast agents and the development of contrast specific ultrasound techniques improved the ability of contrast enhanced ultrasound (CEUS) in detecting and characterizing focal liver lesions, opening new prospects in liver imaging. A Medline search in June 2008 identified 72 published studies that used CEUS in focal liver lesion detection, characterization, and follow-up to monitor tumor ablation procedures and antiangiogenic treatment. The purpose of this paper, based on literature review, is to describe the technical recommendations when using CEUS for liver imaging and to define the different vascular patterns of the most relevant benign and malignant lesions. Diagnostic performance of CEUS and the important clinical indications are also presented and discussed. CEUS is increasingly accepted in clinical use for diagnostic imaging and post-interventional workup liver imaging. It may replace many computed tomography and magnetic resonance imaging examinations in the near future, according to the European Federation of Societies for Ultrasound in Medicine and Biology guidelines.

Intervalence-resonant Raman spectroscopy of strongly coupled mixed-valence cluster dimers of ruthenium.

Resonance Raman spectroelectrochemistry (RR-SEC) at -20 degrees C has been performed on the pyrazine-bridged dimer of mu-oxo-centered trinuclear ruthenium-acetate "clusters"--[(dmap)(CO)(mu-OAc)6(mu3-O)Ru3(mu-L(b))Ru3(mu3-O)(mu-OAc)6(CO)(dmap)]n (where dmap = 4-(dimethylamino)pyridine and L(b) = pyrazine-h4 and pyrazine-d4)-in three oxidation states: n = 0, -1, and -2. In the one-electron reduced, "mixed-valent" state (overall -1 charge and a single odd electron; formal oxidation states [II, II, III]-[III, III, II] on the metal centers), the Raman excitation at 800 nm is resonant with a cluster-to-cluster intervalence charge-transfer (IVCT) band. Under these conditions, scattering enhancement is observed for all four totally symmetric vibrational modes of the bridging pyrazine ligand (nu8a, nu9a, nu1, and nu6a) in the investigated spectral range (100-2000 cm(-1)), and there is no evidence of activity in non-totally symmetric vibrations. Resonantly enhanced Raman peaks related to peripheral pyridyl (dmap) ligand modes and low-frequency features arising from the trigonal Ru3O cluster core and the cluster[Ru]-[N]ligand vibrations were also observed in the spectra of the intermediate-valence (n = -1) cluster dimer. The vibrational assignments and interpretations proposed in this work were reinforced by observation of characteristic isotopic frequency shifts accompanying deuteration of the bridging pyrazine. The results reveal that the fully symmetric (A(g)) vibrational motions of the organic bridge are coupled to the nominally metal cluster-to-metal cluster fast intramolecular electron transfer (ET) and provide validation of the near-delocalized description according to a predicted three-site/three-state (e.g., metal-bridge-metal) vibronic coupling model, in which the important role of the bridging ligand in mediating electronic communication and delocalization between charge centers is explicitly considered. Further compelling evidence supporting an extended five-state model, which incorporates the peripheral cluster-bound pyridyl ligands, is also presented.

Intervalence involvement of bridging ligand vibrations in hexaruthenium mixed-valence clusters probed by resonance Raman spectroscopy.

Resonance Raman spectroscopy, performed using spectroelectrochemistry and with excitation in the intervalence bands of three pyrazine-bridged, mixed-valence dimers of trinuclear ruthenium clusters, shows resonant enhancement of symmetric bridging ligand modes. The resonant enhancements and frequency shifts of these bridging ligand modes are observed as a function of varying electronic communication between charge sites, and they show that a three-state vibronic model which explicitly includes the participation of the bridging ligand is needed to explain the spectroscopic behavior of these near-delocalized complexes.

Electrochemical and spectroscopic characterization of the novel charge-transfer ground state in diimine complexes of ytterbocene.

The novel charge-transfer ground state found in alpha,alpha'-diimine adducts of ytterbocene (C(5)Me(5))(2)Yb(L) [L = 2,2'-bipyridine (bpy) and 1,10-phenanthroline (phen)] in which an electron is spontaneously transferred from the f(14) metal center into the lowest unoccupied (pi*) molecular orbital (LUMO) of the diimine ligand to give an f(13)-L(*)(-) ground-state electronic configuration has been characterized by cyclic voltammetry, UV-vis-near-IR electronic absorption, and resonance Raman spectroscopies. The voltammetric data demonstrate that the diimine ligand LUMO is stabilized and the metal f orbital is destabilized by approximately 1.0 V each upon complexation for both bpy and phen adducts. The separation between the ligand-based oxidation wave (L(0/-)) and the metal-based reduction wave (Yb(3+/2+)) in the ytterbocene adducts is 0.79 V for both bpy and phen complexes. The UV-vis-near-IR absorption spectroscopic data for both the neutral adducts and the one-electron-oxidized complexes are consistent with those reported recently, but previously unreported bands in the near-IR have been recorded and assigned to ligand (pi*)-to-metal (f orbital) charge-transfer (LMCT) transitions. These optical electronic excited states are the converse of the ground-state charge-transfer process (e.g., f(13)-L(*-) <--> f(14)-L(0)). These new bands occur at approximately 5000 cm(-1) in both adducts, consistent with predictions from electrochemical data, and the spacings of the resolved vibronic bands in these transitions are consistent with the removal of an electron from the ligand pi* orbital. The unusually large intensity observed in the f --> f intraconfiguration transitions for the neutral phenanthroline adduct is discussed in terms of an intensity-borrowing mechanism involving the low-energy LMCT states. Raman vibrational data clearly reveal resonance enhancement for excitation into the low-lying pi* --> pi* ligand-localized excited states, and comparison of the vibrational energies with those reported for alkali-metal-reduced diimine ligands confirms that the ligands in the adducts are reduced radical anions. Differences in the resonance enhancement pattern for the modes in the bipyridine adduct with excitation into different pi* --> pi* levels illustrate the different nodal structures that exist in the various low-lying pi* orbitals.